Brown azo dyestuffs



Patented July 12, 1932 cit/V FFECE 'W'ISCONTSIN, ASSZGNOR- '20 E. I. DI)" POITT DE ll ZOURS dz. GOHZPAETY, OF WILMZNGTON, BELAWARE, A CORPORATION OF DELA- ERGWEJ AZO DYES'IUFFS No Drawing.

7 n 1931 of which this ap- L disclosed tetrakisazo dyestun form of their free cids the eral formula:

soin

CH3 V I I which he pher lenc residues H and may be tree or en i uted by like or difiermonovalent suostituents, other than sulionic acid groups, for instance, alkyl or al. :oxy groups. These dyestulls were found by me to possess the above mentioned desired characterist'cs to a remarkable degree. In other Words, dyestuiis represent-ed by this neric formula produce upon cotton,

ather a neutral or alkaline bath, yellowish brown to reddish brown shades of good brightness and of excellent fastness to light and to Washing.

Application filed February 15, 1932. Serial No. 593,212.

wherein the phenylene residues II and H I be free or substituted, as in the precedcase, by like or different monovalent substituents other than sullonic acids, for instance alkyd or alkoxy groups.

t will be noted that the dyestuffs of my novel and v ider series have the same general constitution as the dyestuffs in the parent application, except that the choice of first componentis not limited to 2-naphthylamine-6, S-disulfonio acid. Instead, any other 2- n'aphthylamine-disulfonic acid may be used, for instance, Q-naphthylaminel,8-disulfonic acid, 2-naphthylamine-3,8-disulfonic acid, 2 aphthylamine-3,G-disulionic acid, or 2- naphthylamine-o,7-disulfonic acid.

I am aware that urea-type tetrakisazo dyestuffs in general are known and have been described, for example, in U. S. Patent- No. 978,580. Although" U. S. Patent No. 978,580 indicates that some of the combinations disclosed would yield brown shades, it Was not to be foreseen that the particular combination herein disclosed and claimed would give shades of a brightness heretofore not general ly found in connection with brown colors. In fact, many of the combinations coming Within the broad disclosure of U. S. Patent No. 978,580 give shades which, if brown at all, are dull and of little commercial value.

Also, the dyestuffs of my novel series are characterized in general by lighter shades of brown than obtainable from corresponding dyestuffs having a cresidine residue as third component in lieu of a meta-toluidine residue.

My preferred method of preparing my new dyestuffs comprises diazotizing a Q-naphthylamine-disulfonic acid, coupling the diazo body thus formed to aniline or a substitution derivative of aniline having a free position para to the amino group and containing no sulfonic acid groups, rediazotizing the amino azo body and coupling the diazo body last formed to meta-toluidine, and finally condensing the resulting amino-disazo dyestuff according to well known procedure with phosgene to produce a urea-type tetrakisazo dyestufl'.

The intermediate amino-disazo dyestuffs above obtained possess in the form of their free acids the following general formula:

wherein the middle component may carry other substituents, for instance alkyl or alkoxy, but no sulfonic acid groups.

In condensing with phosgene, I may use either an amino disazo dyestuff of the above general formula by itself, in which case the resulting condensation product is uniformly composed of a symmetrical ureaof the type (A standing for the formula of an aminodisazo dyestuff of the above general type, minus the right hand NH group) or I may use a substantially equimolecular mixture of two amino-disazo compounds of the above general formula, in which case the resulting dyestuff contains to a large extent an unsymmetrical urea of the type (A and B standing for the formulas of two different amino-disazo dyestuffs of the above general type, minus the right-hand NH groups).

If unsubstituted aniline is selected as the middle component in the above general formula, the resulting condensation product dyes cotton in yellowish brown shades. If cresidine is selected, the shade is reddish brown. If less heavily substituted intermediates are selected, for instance, those containing meta-toluidine, para-Xylidine, or ortho-anisidine as the second component, intermediate brown shades maybe produced. Similar intermediate brown shades may also be produced if a mixture of any two of the above defined intermediates is selected. In

'- all cases, the brightness of the shade, its exhausting qualities, and its good fastness to light and to washing are remarkable.

My novel dyestuffs are isolated in the form of an alkali metal salt, generally the sodium salt; and may be used to dye cotton directly from either a neutral or an alkaline bath.

The following specific examples will serve further to illustrate my invention. But it is to be understood that my invention is not limited to the precise details indicated below. The parts given are by weight.

Eazample 1 303 parts of 2-amino-naphthalene-6,8-disulfonic acid are dissolved in 3000 parts of water and the mixture is made slightly alkaline with soda ash. 464: parts of hydrochloric acid (20 B.) and 69 parts of sodium nitrite are now added and diazotization is completed at a temperature of 0 to 5 C.

To this diazo mixture 400 parts of sodium acetate (crystals) are added, together with 209 parts of methylaniline-omega-sulfonic acid. The coupling is finished in 5 to hours and the resulting mass is made strongly alkaline with caustic soda or any other suitable alkaline hydrolyzing agent, boiled, salted out Be.) and filtered. The paste of the resulting amino-azo compound is dissolved in 3000 parts of water, made acid with 320 parts of hydrochloric acid (20 Be.) and diazotized with l9 parts of nitrite of soda at a temperature of 10 C. 85 parts of meta-toluidine dissolved in 1000 parts of water and 90 parts of hydrochloric acid (20 B6.) are now added to this diazo mixture and the mineral acid neutralized by the addition of 300 parts of sodium acetate (crystals). The coupling is complete in about 20 hours. The mixture is now rendered acid with hydrochloric acid and filtered.

The resulting amino-disazo dye paste is now dissolved in 3000 parts of water and rendered alkaline, preferably with soda ash. The solution is heated to 7 0 C. and phosgene gas is forced into the solution until condensation of the amino-disazo compound with phosgene is complete. The completeness of this reaction can be determined by testing samples of the mixture for free amine. The solution, during the condensation, must be kept continuously neutral or alkaline by the addition of soda ash.

When the condensation is complete, the dyestuff which has crystallized out of solution is filtered and dried.

The dyestuff when in the dry state is a yellowish brown powder, which dissolves in water with a yellowish brown color, unchanged by the addition of alkali, but assuming a bluish color by the addition of mineral acid. It dyes cotton from a neutral or alkaline bath avery bright yellowish-brown shade, exceptionally fast to light and to washing.

Upon reduction with stannous chloride or hydrosulfite of sodium, the dyestufi yields 2-amino-naphthalene-6,S-disulfonic acid, pphenylene-diamine, and 4,4-diamino-3,3- dimethyl-diphenyl urea.

Eazample 2 The procedure is the same as in Example 1, except that the 209 parts of methyl-anilineomega-sulitonic acid used in that example are replaced by 239 parts of ortho-methoxy-methyl-aniline-omega-sulfonic acid. I

The resulting dyestufl in the dry state is a reddish brown colored powder, which dissolves in water with a reddish brown color unchanged by additions of alkali, but changing to a blue color by the addition of mineral acid. It dyes cotton from a neutral or alkiline bath a bright reddish brown shade which is exceptionally fast to light and to washing.

It the dye is reduced with stannous chloride or with hydrosulfite of sodium, it yields 2 amino naphthalene 6,8 disulfonic acid, methoxy-p phenylene-diamine, and 4,4-diamino-3,3-dimethyl-diphenyl urea.

E sample 3 263 parts of the amino-di aao base obtained in Example 1, and 278 parts of the aminodisazo base obtained in Example 2 are dissolved in l000 parts of water which has been rendered alkaline with soda ash. The solution is heated to C. Phosgene gas is then passed into the solution until the condensation of the amino-disazo bases and the phosgene is complete. The solution must continuously be kept neutral or alkaline with soda ash.

After the condensation is complete, the dye is filtered off and dried. The dyestufi in the dry state is an orange brown powder which dissolves in water with a similar color, remaining unchanged by the addition of alkali, but changing to blue by the addition of acid. It dyes cotton froma neutral or alkaline bath bright brown shades remarkably fast to light and to washing.

Upon reduction with stannous chloride or hydrosulfite of sodium, the dyestutl yields 2- amino-naphthalene-6,8-disultonic acid, pphenylene-diamine, methoxy-p-phenylenediamine and 4,4-diamino-3,3-dimethyl-diphenyl urea.

E mample 4 but assuming a bluish color by the addition of mineral acid. It dyes cotton from a neutral or alkaline bath a very bright yellowishbrown shade, exceptionally fast to light and to washing.

Upon reduction with stannous chloride or hydrosulfite of sodium, the dyestutl yields 2- aminonaphthalene-4,8-disu1tonic acid, pphenylene-diamine and t,4-diamino-3,3'- dimethyl-diphenyl urea.

E mample 5 The procedure is the same as in Example st, except that the 209 parts of methyl-anilineomega-sulfonic acid are replaced by 239 parts of ortho-methoxy-methyl-aniline-omega-sultonic acid.

The resulting dyestull in the dry state is a reddish brown colored powder, which dissolves in Water with a reddish brown color, unchanged by the addition of alkali, but changing to a blue color by the addition of mineral acid. It dyes cotton from a neutral or alkaline bath a bright reddish brown shade which is exceptionally fast to light and to washing.

It the dye is reduced with stannous chlo ride or hydrosulfite of sodium, it yields 2- amino-naphtlialone-4,8-disulfonic acid, methoxy-p-phenylene-diamine, and aft-diam no3,3dimethyl-diphenyl urea.

E example 6 263 parts of amino-disazo base, as obtained in Example 4- and 278 parts of the aminodisazo base as obtained in Example 5 are dissolved in l000 parts of water, which has been rendered alkaline with soda ash. The solution is heated to 70 C. Phosgene gas is then passed into the solution until the condensation of the amino-disazo bases and the phosgene is complete. The solution must continuously be kept neutral or alkaline with soda ash.

After the condensation is complete, the dye is filtered ofi', and dried. The dyestufi in the dry state is an orange brown powder, which dissolves in water with a similar color, remainin unchanged by the addition of alkali, but changing to blue by the addition of mineral acid. t dyes cotton from a neutral or alkaline bath bright brown shades remarkably fast to light and to washing.

Upon reduction with stannous chloride or hydrosulfite of sodium, the dyestuff yields 2- amino-naphthalene- -,8-disulfonic acid, pphenylcnediamine, methoxy-p-phenylenediamine and 4, 1-diamino-3,3-dimethyl-diphenyl urea.

It the same procedure is followed as in Examples 1, 2 and 3, except that the first component, 2amino-naphthalene-6,S-disulfonic acid, is replaced by equal quantities of other Q-amino-naphthalene-disultonic acids, such as the 3,6-, 3,8- or 5,7-disu1'l'onic acids, a variety of brown shades are produced, all possessing the same characteristic property of dyeing cotton exceptionally bright shades of good wash and light fastness.

Mixtures of the above various 2-aminonaphthalene-disulfonic acids may be used, if desired. In this case the product consists largely of an unsymmetrical urea, which differs from the unsymmetrical ureas obtained in Examples 3 and G in the fact that here the first components, or both the first and second components are different from each other. The shades and dyeing qualities of these mixed ureas are, however, substantially the same as those of the corresponding symmetrical dyestuffs.

As stated above, other middle components may be used in preparing the amino-disazo compounds. It will be understood, of course, that where a more active middle component than aniline is selected, for instance, metatoluidine or cresidine, the same may be coupled directly in basic form; that is, without previous conversion into the omega-methylsulfonic acid derivative.

Although the primary utility of my novel brown dyestuffs is in dyeing cotton, it will be understood that they are adapted also for dyeing other materials, for instance, wool, silk and rayon.

In the claims below, it should be understood that where new products, dyestuffs, or articles of manufacture are claimed, I mean to include these bodies not only in substance, but also in whatever state they may exist when applied to material dyed, printed or pigmented therewith.

I am aware that numerous details of the process may be varied through a wide range without departing from the principles of this invention, and I, therefore, do not purpose limiting the patent granted hereon, otherwise than necessitated by the prior art.

I claim as my invention: 1. As a new productof manufacture, a tetrakisazo dyestuff having in the form of its free acid the following probable general (HOaS)2 in which the phenylene residues II and II are free or substituted by like or different substituents of the group consistins of alkyl and alkoxy groups, said dyestufl being characterized by dyeing cotton from a neutral or alkaline bath in yellowish brown to reddish brown shades of great brightness and of good fastness to light and to washing.

,2. As a new product of manufacture a tetrakisazo dyestuif having in the form of its free acid the following probable general in which aand y individually stand for either H or the OCH group, said dyestulf being characterized by dyeing cotton from a neutral or alkaline bath in yellowish brown to reddish brown shades of great brightness and of good fastness to light and to washing.

3. As a new product of manufacture a tetrakisazo dyestuff having in the form of its free acid the following probable formula:

(HOaS)2 said dyestuif being characterized by dyeing cotton from a neutral or alkaline bath a yellowish brown shade of excellent brightness and good fastness to light and to washing.

4:. As a new product of manufacture a tetrakisazo dyestuff having in the form of its free acid the following probable formula N=N-N=N-ONH a A) O H; C H: l

o OCH; OH; (H 0:8)2- v I said dyestuff being characterized by dyeing cotton from a neutral or alkaline bath an orange-brown shade of excellent brightness and good fastnessto light and to washing.

6. As a new product of manufacture, a tetrakisazo dyestuff having in the form of its free acidthe following probable general free acid the following probable general formula:

N=N- II -N=NNH 1103s -SO3H o0 HOaS- so3n E in which the phenylene residues 11 and II are free or substituted by like or different substituents of the group consisting of alkyl and alkoxy groups, said dyestuff being char acterized by dyeing cotton from a neutral or alkaline bath in yellowish brown to recldish brown shades of great brightness and of good fastness to light and to washing.

8. As a new product of manufacture, a

' tetrakisazo d estufi having in tie form of its free acid the following probable general formula:

in which the phenylene residues H and II are free or substituted by like or diilerent substituents of the group consisting of alkyl and allzoxy groups, said dyestuif being characterized by dyeing cotton from a neutral or alkaline bath in yellowish brown to reddish brown shades of great brightness and of good fastness to light and to washing.

9. As a new product of manufacture a tetrakisazo dyestun having in the form of its free acid the following probable formula:

SOaH

said dyestuff being characterized by dyeing cotton from a neutral or alkaline bath a yellowish brown shade of excellent brightness and good fast-mess to light and to washing.

10. As a new product of manufacture a J. L tetr l irisazo dyestuff having in the form of its free acid the following probable formula HOaS sou1 0H3 I I oo nmssour said dyestufi being characterized by dyeing cotton from a neutral or alkaline bath a yellowish brown shade of excellent brightness and good fastn to light and to washing.

11. As a new product of manufacture, a tetrakisazo dyestuff having in the form of its free acid the following probable formula:

said dyestufl being characterized by dyeing cotton from a neutral or-alkaline bath a yellowish brown shade of excellent brightness and good fastiess to light and to washing.

12. The process of preparing a bright brown azo dyestuif, which comprises reacting with phosgene upon an amino-disazo compound which in the form of its free acid has the following probable general formula:

NH: (H035)? in which the middle phenylene nucleus is free or substituted by substituents of the group consisting of alkyl and a-lkoxy, and recovering the product.

13. The process of preparing a bright brown azo dyestuif, which comprises reacting with phosgene upon an amino-disazo compound which in the form of its free acid has the following probable general formula:

in which 00 stands for H or OCH and recovering the product.

14. The process of preparing a bright brown azo dyestu'lf, which comprises reacting with phosgene upon an amino-disazo com pound which in the form of its free acid has the following probable formula:

and recovering the product.

15. The process of preparing a bright brown azo dyestufi, which comprises reacting with phosgene upon an amino-disazo compound which in the form of its free acid has the following probable formula:

and recovering the product.

16. The process of preparing a bright brown azo dyestuff which comprises reacting with phosgene upon a mixture of two aminodisazo compounds having in the form of their free acids the following probable respective formulas:

CHa CH and recovering the product.

17. The process of preparing a bright brown azo dyestuff, which comprises reacting with phosgene upon an amino-disazo compound which in the form of its free acid has the following probable general formula:

SI 0 a H SOaH O S O 3 H OaH in which the middle phenylene nucleus is free or substituted by substituents of the group consisting of alkyl and alkoxy, and recovering the product.

18. The process of preparing a bright brown azo dyestufi, which comprises reacting with phosgene upon an amino-disazo compound which in the form of its free acid has the following probable general formula:

l l l l SOaH in which the middle phenylene nucleus is free or substituted by substituents of the group consisting of alkyl and alkoxy, and recovering the product.

In testimony whereof I afiix my signature.

DANIEL ZINNER.

HOaS 

